波谱学杂志 ›› 2021, Vol. 38 ›› Issue (3): 301-312.doi: 10.11938/cjmr20212893

• 研究论文 • 上一篇    下一篇

正丁醇/丙酸与腐殖酸相互作用的NMR研究

张书怀1,2,马慧1,2,郭朝晖1,2,马敏珺1,2,乔岩1,2,*(),王英雄1,2,*()   

  1. 1. 中国科学院 山西煤炭化学研究所, 山西 太原 030001
    2. 中国科学院大学 材料与光电研究中心, 北京 100049
  • 收稿日期:2021-02-28 出版日期:2021-09-05 发布日期:2021-03-31
  • 通讯作者: 乔岩,王英雄 E-mail:qiaoy@sxicc.ac.cn;wangyx@sxicc.ac.cn
  • 基金资助:
    国家自然科学基金资助项目(U1710106)

Interactions Between n-Butanol/Propionic Acid and Humic Acid Studied by NMR Spectroscopy

Shu-huai ZHANG1,2,Hui MA1,2,Zhao-hui GUO1,2,Min-jun MA1,2,Yan QIAO1,2,*(),Ying-xiong WANG1,2,*()   

  1. 1. Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
    2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2021-02-28 Online:2021-09-05 Published:2021-03-31
  • Contact: Yan QIAO,Ying-xiong WANG E-mail:qiaoy@sxicc.ac.cn;wangyx@sxicc.ac.cn

摘要:

由于制备液体燃料的费托合成工艺在合成过程中排放的费托反应生成水通常含有水溶性含氧化合物,例如醇、醛、酮和羧酸.费托反应生成水酸性强、成分复杂、种类繁多,因此需处理后才能排放.本文以核磁共振(NMR)为主要技术手段,以正丁醇和丙酸作为费托反应生成水中水溶性有机成分的模型化合物,研究了腐殖酸(HA)对费托反应生成水的吸附作用.1H NMR滴定实验和1H弛豫时间测定结果显示:随HA浓度增大,正丁醇质子信号变宽,但化学位移未变;丙酸质子信号变宽,且化学位移向高场移动;正丁醇和丙酸的1H自旋-晶格和自旋-自旋弛豫时间均降低,分子相关时间增大.HA与正丁醇、丙酸的结合百分比表明HA对正丁醇的吸附作用大于丙酸.增加HA浓度有利于HA与正丁醇相互作用,但溶液pH值对HA(20 mg/mL)与正丁醇相互作用影响较小;另一方面,增加HA浓度、降低溶液pH值均有利于HA与丙酸相互作用,且HA浓度对相互作用的影响高于溶液pH值.本研究表明HA用于吸附处理费托反应生成水有效,且过程简单、价格低廉,在工业应用中具有潜力.

关键词: 液体核磁共振, 吸附, 费托反应生成水, 腐殖酸, 正丁醇, 丙酸

Abstract:

The Fischer-Tropsch process produces liquid fuels. However, the process also yields Fischer-Tropsch wastewater, an acidic and corrosive byproduct enriched with various water-soluble oxygen-containing compounds such as alcohols, aldehydes, ketones and carboxylic acids, demanding careful treatment before discharge. Herein, the interactions between n-butanol and propionic acid, two main components in Fischer-Tropsch wastewater, and humic acid (HA) were studied with nuclear magnetic resonance (NMR) techniques. One-dimensional 1H chemical shift titration and 1H relaxation time measurements showed that: the peak width of both n-butanol and propionic acid broadened with increasing HA concentration, while the 1H chemical shift was unaltered for n-butanol, but moved to high field for propionic acid. The 1H spin-lattice and spin-spin relaxation time of n-butanol and propionic acid decreased and the 1H correlation time increased with increasing HA concentration. The interactions between HA and n-butanol were enhanced by increasing the HA concentration, but less affected by solution pH. While, the interactions between HA (20 mg/mL) and propionic acid were promoted by increasing the HA concentration and decreasing the solution pH value. It also appeared that the HA concentration plays a decisive role in the interaction. The study demonstrated that using HA for treatment of Fischer-Tropsch wastewater has a great potential in industrial applications owing to its simplicity and low price.

Key words: liquid-state NMR, adsorption, Fischer-Tropsch wastewater, humic acid, n-butanol, propionic acid

中图分类号: